Impact of biosolids on the persistence and dissipation pathways of triclosan and triclocarban in an agricultural soil

The broad spectrum antimicrobial agents triclosan (TCS) and triclocarban (TCC) are widely used in many personal care products. Knowledge concerning the fate of these two compounds in different environmental matrices is scarce. In this study, the fate of TCS and TCC in soil following direct addition, or when residues were applied via either liquid municipal biosolids (LMB) or dewatered municipal biosolids (DMB) was investigated in laboratory dissipation experiments and under outdoor conditions using radioisotope methods. In laboratory incubations, ¹⁴C-TCC or ¹⁴C-TCS was added to microcosms containing a loam soil and the rate of ¹⁴CO₂ accumulation and loss of solvent-extractable ¹⁴C were determined during incubation at 30 °C. Compared to when TCC or TCS was added directly to soil, both chemicals were mineralized more rapidly when applied in LMB, and both were mineralized more slowly when applied in DMB. The application matrix had no effect on the rate of removal of extractable residues. In field experiments, parent compounds were incorporated directly in soil, incorporated via LMB, or a single aggregate of amended DMB was applied to the soil surface. During the experiment soil temperatures ranged from 20 °C to 10 °C. Dissipation was much slower in the field than in the laboratory experiments. Removal of non-extractable residues was faster in the presence of LMB than the other treatments. Recovery of extractable and non-extractable residues suggested that there was little atmospheric loss of ¹⁴C. Triclocarban readily formed non-extractable residues with DMB whereas TCS did not. Overall, this study has identified that both the pathways and the kinetics of TCS and TCC dissipation in soil are different when the chemicals are carried in biosolids compared to when these chemicals are added directly to the soil.     

Phytoaccumulation of antimicrobials from biosolids: impacts on environmental fate and relevance to human exposure

Triclocarban and triclosan, two antimicrobials widely used in consumer products, can adversely affect ecosystems and potentially impact human health. The application of biosolids to agricultural fields introduces triclocarban and triclosan to soil and water resources. This research examined the phytoaccumulation of antimicrobials, effects of plant growth on migration of antimicrobials to water resources, and relevance of phytoaccumulation in human exposure to antimicrobials. Pumpkin, zucchini, and switch grass were grown in soil columns to which biosolids were applied. Leachate from soil columns was assessed every other week for triclocarban and triclosan. At the end of the trial, concentrations of triclocarban and triclosan were determined for soil, roots, stems, and leaves. Results indicated that plants can reduce leaching of antimicrobials to water resources. Pumpkin and zucchini growth significantly reduced soil concentrations of triclosan to less than 0.001 mg/kg, while zucchini significantly reduced soil concentrations of triclocarban to 0.04 mg/kg. Pumpkin, zucchini, and switch grass accumulated triclocarban and triclosan in mg per kg (dry) concentrations. Potential human exposure to triclocarban from consumption of pumpkin or zucchini was substantially less than exposure from product use, but was greater than exposure from drinking water consumption. Consequently, research indicated that pumpkin and zucchini may beneficially impact the fate of antimicrobials in agricultural fields, while presenting minimal acute risk to human health.     

Fate of Triclocarban,Triclosan and Methyltriclosan during wastewater and biosolids treatment processes

Triclocarban (TCC) and Triclosan (TCS) are two antibacterial chemicals present in household and personal care products. Methyltriclosan is a biodegradation product of TCS formed under aerobic conditions. TCC and TCS are discharged to Waste Water Treatment Plants (WWTP) where they are removed from the liquid phase mainly by concentrating in the solids. This study presents a thorough investigation of TCC, TCS and MeTCS concentrations in the liquid phase (dissolved + particulate) as well as solid phases within a single, large WWTP in the U.S. Total TCC and TCS concentrations decreased by >97% with about 79% of TCC and 64% of TCS transferred to the solids. The highest TCC and TCS removal rates from the liquid phase were reached in the primary treatment mainly though sorption and settling of solids. The TCC mass balances showed that TCC levels remain unchanged through the secondary treatment (activated sludge process) and about an 18% decrease was observed through the nitrification–denitrification process. On the other hand, TCS levels decreased in both processes (secondary and nitrification–denitrification) by 10.4 and 22.6%, respectively. The decrease in TCS levels associated with observed increased levels of MeTCS in secondary and nitrification–denitrification processes providing evidence of TCS biotransformation. Dissolved-phase concentrations of TCC and TCS remained constant during filtration and disinfection. TCC and TCS highest sludge concentrations were analyzed in the primary sludge (13.1 ± 0.9 μg g^?1 dry wt. for TCC and 20.3 ± 0.9 μg g^?1 dry wt. for TCS) but for MeTCS the highest concentrations were analyzed in the secondary sludge (0.25 ± 0.04 μg g^?1 dry wt.). Respective TCC, TCS and MeTCS concentrations of 4.15 ± 0.77; 5.37 ± 0.97 and 0.058 ± 0.003 kg d^?1 are leaving the WWTP with the sludge and 0.13 ± 0.01; 0.24 ± 0.07 and 0.021 ± 0.002 kg d^?1 with the effluent that is discharged.     

Pharmaceutical and personal care products in tile drainage following land application of municipal biosolids

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p<0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.     

Runoff of pharmaceuticals and personal care products following application of dewatered municipal biosolids to an agricultural field

Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m² microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L^− 1 (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (< 1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (> 1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K_ow values of 3.18 or greater, whereas those that were readily mobilized had K_ow values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K_ow may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.     

Investigation of the tetracycline, sulfonamide, and fluoroquinolone antimicrobial compounds in animal manure and agricultural soils in Turkey

Occurrence of antimicrobial residuals in the environment is of concern because of the emergence and development of antimicrobial-resistance in pathogen bacteria, and the ecotoxicological behaviour of these compounds. Investigation of antimicrobial pollution in animal manure has special importance since they constitute the major source for the dissemination of these chemicals into the environment. Hence, eight animal manure and nine agricultural soil samples from the North part of Marmara Region (Turkey) were collected and analyzed for two tetracyclines (TCs), four sulfonamides (SAs), and two fluoroquinolones (FQs). At least one antimicrobial compound was detected in all the agricultural soil and animal manure samples. The highest antimicrobial concentrations were in general detected in the fresh poultry manure samples. Mean recoveries from spiked soil and manure samples ranged from 60 to 86% and 62 to 77% for TCs, 69 to 101% and 14 to 82% for SAs, and 46 to 55% and 24 to 42% for FQs, respectively. Relationship between the recovery rates of the antimicrobial compounds and sample characteristics was statistically evaluated by means of hierarchical cluster analysis (HCA), and principal component analysis (PCA) followed by multiple stepwise regression (MSR). HCA showed agricultural soil samples with higher di- and trivalent metal contents resulted in higher TC and lower FQ recoveries. TC recoveries from manure were highest in the samples with lowest K, Mg, and Ca content, while FQs were more efficiently extracted from the manure samples with less % organic carbon (OC) content. The findings of HCA for TCs were supported by those of MSR analysis, giving comparable results. In addition, MSR of SA recoveries revealed that the increasing amounts of manure % OC led to lower recoveries.     

Runoff of pharmaceuticals and personal care products following application of biosolids to an agricultural field

Municipal biosolids are a source of nutrients for crop production. Beneficial Management Practices (BMPs) can be used to minimize the risk of contamination of adjacent water resources with chemical or microbial agents that are of public or environmental health concern. In this field study, we applied biosolids slurry at a commercial rate using either subsurface injection or broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 22, 36 and 266 days post-application on 2 m² microplots to evaluate surface runoff of 9 model pharmaceuticals and personal care products (PPCPs), atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole and triclosan. In runoff from the injected plots, concentrations of the model PPCPs were generally below the limits of quantitation. In contrast, in the broadcast application treatment, the concentrations of atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, sulfamethoxazole and triclosan on the day following application ranged from 70-1477 ng L^− 1 in runoff and generally declined thereafter with first order kinetics. The total mass of PPCPs mobilized in surface runoff per m² of the field ranged from 0.63 µg for atenolol to 21.1 µg for ibuprofen. For ibuprofen and acetaminophen, concentrations in runoff first decreased and then increased, suggesting that these drugs were initially chemically or physically sequestered in the biosolids slurry, and subsequently released in the soil. Carbamazepine and triclosan were detected at low concentrations in a runoff event 266 days after broadcast application. Overall, this study showed that injection of biosolids slurry below the soil surface could effectively eliminate surface runoff of PPCPs.     

Pharmaceutical and personal care products in tile drainage following surface spreading and injection of dewatered municipal biosolids to an agricultural field

Land application of municipal biosolids can be a source of environmental contamination by pharmaceutical and personal care products (PPCPs). This study examined PPCP concentrations/temporally discrete mass loads in agricultural tile drainage systems where two applications of biosolids had previously taken place. The field plots received liquid municipal biosolids (LMB) in the fall of 2005 at an application rate of ∼ 93,500 L ha^− 1, and a second land application was conducted using dewatered municipal biosolids (DMB) applied at a rate of ∼ 8 Mt dw ha^− 1 in the summer of 2006. The DMB land application treatments consisted of direct injection (DI) of the DMB beneath the soil surface at a nominal depth of ∼ 0.11 m, and surface spreading (SS) plus subsequent tillage incorporation of DMB in the topsoil (∼ 0.10 m depth). The PPCPs examined included eight pharmaceuticals (acetaminophen, fluoxetine, ibuprofen, gemfibrozil, naproxen, carbamazepine, atenolol, sulfamethoxazole), the nicotine metabolite cotinine, and two antibacterial personal care products triclosan and triclocarban. Residues of naproxen, cotinine, atenolol and triclosan originating from the fall 2005 LMB application were detected in tile water nearly nine months after application (triclocarban was not measured in 2005). There were no significant differences (p > 0.05) in PPCP mass loads among the two DMB land application treatments (i.e., SS vs. DI); although, average PPCP mass loads late in the study season (> 100 days after application) were consistently higher for the DI treatment relative to the SS treatment. While the concentration of triclosan (∼ 14,000 ng g^− 1 dw) in DMB was about twice that of triclocarban (∼ 8000 ng g^− 1 dw), the average tile water concentrations for triclosan were much higher (43 ± 5 ng L^− 1) than they were for triclocarban (0.73 ± 0.14 ng L^− 1). Triclosan concentrations (maximum observed in 2006 ∼ 235 ng L^− 1) in tile water resulting from land applications may warrant attention from a toxicological perspective.     

Polybrominated diphenyl ethers, perfluorinated alkylated substances, and metals in tile drainage and groundwater following applications of municipal biosolids to agricultural fields

Polybrominated diphenyl ethers (PBDEs), perfluorinated alkylated substances (PFAS), and metals were monitored in tile drainage and groundwater following liquid (LMB) and dewatered municipal biosolid (DMB) applications to silty-clay loam agricultural field plots. LMB was applied (93,500 L ha^− 1) in late fall 2005 via surface spreading on un-tilled soil (SS_LMB), and a one-pass aerator-based pre-tillage prior to surface spreading (AerWay SSD) (A). The DMB was applied (8 Mg dw ha^− 1) in early summer 2006 on the same plots by injecting DMB beneath the soil surface (DI), and surface spreading on un-tilled soil (SS_DMB). Key PBDE congeners (BDE-47, -99, -100, -153, -154, -183, -209) comprising 97% of total PBDE in LMB, had maximum tile effluent concentrations ranging from 6 to 320 ng L^− 1 during application-induced tile flow. SS_LMB application-induced tile mass loads for these PBDE congeners were significantly higher than those for control (C) plots (no LMB) (p < 0.05), but not A plots (p > 0.05). PBDE mass loss via tile (0-2 h post-application) as a percent of mass applied was ~ 0.04-0.1% and ~ 0.8-1.7% for A and SS_LMB, respectively. Total PBDE loading to soil via LMB and DMB application was 0.0018 and 0.02 kg total PBDE ha^− 1 yr^− 1, respectively. Total PBDE concentration in soil (0-0.2 m) after both applications was 115 ng g^− 1 dw, (sampled 599 days and 340 days post LMB and DMB applications respectively). Of all the PFAS compounds, only PFOS (max concentration = 17 ng L^− 1) and PFOA (12 ng L^− 1) were found above detectable limits in tile drainage from the application plots. Mass loads of metals in tile for the LMB application-induced tile hydrograph event, and post-application concentrations of metals in groundwater, showed significant (p < 0.05) land application treatment effects (SS_LMB > A > C for tile and SS_LMB and A > C for groundwater for most results). Following DMB application, no significant differences in metal mass loads in tile were found between SS_DMB and DI treatments (PBDE/PFAS were not measured). But for many metals (Cu, Se, Cd, Mo, Hg and Pb) both SS_DMB and DI loads were significantly higher than those from C, but only during < 100 days post DMB application. Clearly, pre-tilling the soil (e.g., A) prior to surface application of LMB will reduce application-based PBDE and metal contamination to tile drainage and shallow groundwater. Directly injecting DMB in soil does not significantly increase metal loading to tile drains relative to SS_DMB, thus, DI should be considered a DMB land application option.     

Kinetics of triclosan oxidation by aqueous ozone and consequent loss of antibacterial activity: relevance to municipal wastewater ozonation

Oxidation of the antimicrobial agent triclosan by aqueous ozone (O(3)) was investigated to determine associated reaction kinetics, reaction site(s), and consequent changes in antibacterial activity of triclosan. Specific second-order rate constants, k(O(3)), were determined for reaction of O(3) with each of triclosan's acid-base species. The value of k(O(3)) determined for neutral triclosan was 1.3(+/-0.1)x10(3)M(-1)s(-1), while that measured for anionic triclosan was 5.1(+/-0.1)x10(8)M(-1)s(-1). Consequently, triclosan reacts very rapidly with O(3) at circumneutral pH (the pH-dependent, apparent second-order rate constant, K(app,O(3)) , is 3.8x10(7)M(-1)s(-1) at pH 7). The pH-dependence of K(app,O(3)) and comparison of triclosan reactivity toward O(3) with that of other phenolic compounds indicates that O(3) reacts initially with triclosan at the latter's phenol moiety. k(O(3)) values for neutral and anionic triclosan were successfully related to phenol ring substituent effects via Brown-Okamoto correlation with other substituted phenols, consistent with electrophilic attack of the triclosan phenol ring. Biological assay of O(3)-treated triclosan solutions indicates that reaction with O(3) yields efficient elimination of triclosan's antibacterial activity. In order to evaluate the applicability of these observations to actual wastewaters, triclosan oxidation was also investigated during ozonation of effluent samples from two conventional wastewater treatment plants. Nearly 100% triclosan depletion was achieved for a 4 mg/L(8.3x10(-5)mol/L)O(3) dose applied to a wastewater containing 7.5 mg/L of DOC, and approximately 58% triclosan depletion for dosage of 6 mg/L(1.3x10(-4)mol/L)O(3) to a wastewater containing 12.4 mg/L of DOC. At O(3) doses greater than 1mg/L(2.1x10(-5)mol/L), hydroxyl radical reactions accounted for <35% of observed triclosan losses in these wastewaters, indicating that triclosan oxidation was due primarily to the direct triclosan-O(3) reaction. Thus, ozonation appears to present an effective means of eliminating triclosan's antibacterial activity during wastewater treatment.     

Formation of bromo-substituted triclosan during chlorination by chlorine in the presence of trace levels of bromide

The side reactions of triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, TC) and chlorine in the presence of sodium chloride were investigated. In the absence of sodium chloride, three chloro-derivatives of TC, 2',3,4,4'-tetrachloro-2-hydroxydiphenyl ether (3-Cl-TC), 2',4,4',5-tetrachloro-2-hydroxydiphenyl ether (5-Cl-TC), and 2',3,4,4',5-pentachloro-2-hydroxydiphenyl ether (3,5-Cl(2)-TC) were formed, whereas in the presence of sodium chloride, 3-bromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (3-Br-TC), 5-bromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (5-Br-TC), (3 or 5)-bromo-2',4,4',(5 or 3)-chloro-2-hydroxydiphenyl ether ((3,5)-(BrCl)-TC), and 3,5-dibromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (3,5-Br(2)-TC) were additionally formed. Radiochemical neutron activation analysis indicated that 1g of commercially available sodium chloride contained 73 microg of bromide and the bromide ion was determined to be the source of the side reactions. The rate of decrease of TC due to reaction with chlorine was greatly accelerated by the presence of bromide ion in the system: the rate with only 1 x 10(-5) M bromide ion was three times the rate in the absence of bromide.     

Distribution of antidepressant residues in wastewater and biosolids following different treatment processes by municipal wastewater treatment plants in Canada

The fate of 14 antidepressants along with their respective N-desmethyl metabolites and the anticonvulsive drug carbamazepine (CBZ) was studied in 5 different sewage treatment plants (STPs) across Canada. Using two validated LC-MS/MS analytical methods, the concentrations of the different compounds were determined in raw influent, final effluent and treated biosolids samples. Out of the 15 compounds investigated, 13 were positively detected in most 24-h composite raw influent samples. Analysis showed that venlafaxine (VEN), its metabolite O-desmethylvenlafaxine (DVEN), citalopram (CIT), and CBZ were detected at the highest concentrations in raw influent (up to 4.3 μg L⁻¹ for DVEN). Cumulated results showed strong evidence that primary treatment and trickling filter/solids contact has limited capacity to remove antidepressants from sewage, while activated sludge, biological aerated filter, and biological nutrient removal processes yielded moderate results (mean removal rates: 30%). The more recalcitrant compounds to be eliminated from secondary STPs were VEN, DVEN and CBZ with mean removal rates close to 12%. Parent compounds were removed to a greater degree than their metabolites. The highest mean concentrations in treated biosolids samples were found for CIT (1033 ng g⁻¹), amitriptyline (768 ng g⁻¹), and VEN (833 ng g⁻¹). Experimental sorption coefficients (K_d) were also determined. The lowest K_d values were obtained with VEN, DVEN, and CBZ (67-490 L kg⁻¹). Sorption of these compounds on solids was assumed negligible (log K_d ≤ 2). However, important sorption on solids was observed for sertraline, desmethylsertraline, paroxetine and fluoxetine (log K_d > 4).     

Comparative microscale analysis of the effects of triclosan and triclocarban on the structure and function of river biofilm communities

The broad spectrum antimicrobials triclosan (TCS) and triclocarban (TCC) are commonly detected in the environment. However, there is very limited understanding of the aquatic ecological implications of these agents. During this study, river biofilms were cultivated using 10 µg l^− 1 of TCS or TCC and the equivalent in nutrients (carbon, nitrogen) over a developmental period of 8 weeks. Confocal laser microscopy showed that the biofilm communities developing under the influence of TCS and TCC had community architecture and composition different from either control or nutrient exposed communities. Microscale analyses of biofilm community structure indicated a significant reduction in algal biomass (p < 0.05) as a result of exposure to either TCS or TCC. Thymidine incorporation did not detect significant differences between control and treated communities. The use of carbon utilization assays based on growth indicated that, in general, TCS and TCC suppressed utilization. The community was altered from one dominated by autotrophic processes to one dominated by heterotrophic processes. Both TCS and TCC treatments resulted in significant (p < 0.05) alterations in the composition of the EPS matrix of the communities, suggesting significant changes in community composition. Denaturing gradient gel electrophoresis and PCA-ANOSIM analyses indicated a significant change occurred in the bacterial community as a consequence of TCS treatments. Enumeration of micrometazoa and protozoa revealed an increase in micrometazoan numbers over control values, whereas no clear impact on protozoa was detected in any treatment. This study indicated significant effects of 10 µg l^− 1 TCS and TCC on microbial community composition, algal biomass, architecture and activity.     

Enhanced transformation of triclosan by laccase in the presence of redox mediators

Triclosan (TCS), an antimicrobial agent, is an emerging and persistent environmental pollutant that is often found as a contaminant in surface waters and sediments; hence, knowledge of its degradability is important. In this study we investigated laccase-mediated TCS transformation and detoxification, using laccase (from the fungus Ganoderma lucidum) in the presence and absence of redox mediators. Transformation products were identified using HPLC, ESI-MS and GC-MS, and transformation mechanisms were proposed. In the absence of redox mediator, 56.5% TCS removal was observed within 24 h, concomitant with formation of new products with molecular weights greater than that of TCS. These products were dimers and trimers of TCS, as confirmed by ESI-MS analysis. Among the various mediators tested, 1-hydroxybenzotriazole (HBT) and syringaldehyde (SYD) significantly enhanced TCS transformation (∼90%). The presence of these mediators resulted in products with lower molecular weights than TCS, including 2,4-dichlorophenol (2,4-DCP; confirmed by GC-MS) and dechlorinated forms of 2,4-DCP. When SYD was used as the mediator, dechlorination resulted in 2-chlorohydroquinone (2-CHQ). Bacterial growth inhibition studies revealed that laccase-mediated transformation of TCS effectively decreased its toxicity, with ultimate conversion to less toxic or nontoxic products. Our results confirmed the involvement of two mechanisms of laccase-catalyzed TCS removal: (i) oligomerization in the absence of redox mediators, and (ii) ether bond cleavage followed by dechlorination in the presence of redox mediators. These results suggest that laccase in combination with natural redox mediator systems may be a useful strategy for the detoxification and elimination of TCS from aqueous systems.     

Identification of methyl triclosan and halogenated analogues in male common carp (Cyprinus carpio) from Las Vegas Bay and semipermeable membrane devices from Las Vegas Wash, Nevada

Methyl triclosan and four halogenated analogues have been identified in extracts of individual whole-body male carp (Cyprinus carpio) tissue that were collected from Las Vegas Bay, Nevada, and Semipermeable Membrane Devices (SPMD) that were deployed in Las Vegas Wash, Nevada. Methyl triclosan is believed to be the microbially methylated product of the antibacterial agent triclosan (2, 4, 4'-trichloro-4-hydroxydiphenyl ether, Chemical Abstract Service Registry Number 3380-34-5, Irgasan DP300). The presence of methyl triclosan and four halogenated analogues was confirmed in SPMD extracts by comparing low- and high-resolution mass spectral data and Kovats retention indices of methyl triclosan with commercially obtained triclosan that was derivatized to the methyl ether with ethereal diazomethane. The four halogenated analogues of methyl triclosan detected in both whole-body tissue and SPMD extracts were tentatively identified by high resolution mass spectrometry. Methyl triclosan was detected in all 29 male common carp from Las Vegas Bay with a mean concentration of 596 μg kg^− 1 wet weight (ww) which is more than an order of magnitude higher than previously reported concentrations in the literature. The halogenated analogs were detected less frequently (21%-76%) and at much lower concentrations (< 51 μg kg^− 1 ww). None of these compounds were detected in common carp from a Lake Mead reference site in Overton Arm, Nevada.     

Modelling of the long-term fate of pesticide residues in agricultural soils and their surface exchange with the atmosphere: Part II. Projected long-term fate of pesticide residues

In the first part of this paper, a simple coupled dynamic soil-atmosphere model for studying the gaseous exchange of pesticide soil residues with the atmosphere is described and evaluated by comparing model results with published measurements of pesticide concentrations in air and soil. In Part II, the model is used to study the concentration profiles of pesticide residues in both undisturbed and annually tilled agricultural soils. Future trends are estimated for the measured air and soil concentrations of lindane and six highly persistent pesticides (toxaphene, p,p'-DDE, dieldrin, cis- and trans-chlordane and trans-nonachlor) over a twenty-year period due to volatilization and leaching into the deeper soil. Wet deposition and particle associated pesticide deposition (that increase soil residue concentrations) and soil erosion, degradation in the soil (other than for lindane) and run-off in precipitation are not considered in this study. Estimates of the rain deposition fluxes are reported that show that, other than for lindane, net volatilization fluxes greatly exceed rain deposition fluxes. The model shows that the persistent pesticides studied are highly immobile in soil and that loss of these highly persistent residues from the soil is by volatilization rather than leaching into the deeper soil. The soil residue levels of these six pesticides are currently sources of net volatilization to the atmosphere and will remain so for many years. The maximum rate of volatilization from the soil was simulated by setting the atmospheric background concentration to zero; these simulations show that the rates of volatilization will not be significantly increased since soil resistance rather than the atmospheric concentration controls the volatilization rates. Annual tilling of the soils increases the volatilization loss to the atmosphere. Nonetheless, the model predicts that, if only air-soil exchange is considered, more than 76% of current persistent pesticide residues will remain after 20 years in the top 7 cm of annually tilled soils. In contrast, lindane is relatively mobile in soil due to weaker binding to soil carbon and leaching of lindane into soil is the main removal route for current lindane residues near the soil surface. The model predicts that the soil is a sink for lindane in the atmosphere and that soil residue levels of lindane in the surface soil are determined by a balance between dry gaseous deposition to the soil from the atmosphere and leaching from the surface soil into the deeper soil where degradation is the dominant loss route. The model suggests that deposition of lindane from the atmosphere will sustain residues in the soil and, in the absence of fresh applications of lindane to the soil, eliminating lindane from the atmosphere would lead to a rapid decline of lindane residues in agricultural soils of the southern U.S.     

Distribution of uranium in soil components of agricultural fields after long-term application of phosphate fertilizers

Long-term application of phosphate fertilizers causes accumulation of U in the surface soil of agricultural fields. We investigated the soil constituents that contribute to the accumulation of U by using chemical extraction methods. Surface soil samples were obtained from upland fields, pastures, and paddy fields cultivated without any phosphate fertilizer (control site), with NPK fertilizer (NPK site), and with both NPK fertilizer and compost (NPK + compost site) for more than 20 years. In addition to the total U (U_t) concentration in soil, the concentrations of pyrophosphate- and acid oxalate-extractable U were determined as a measure of U associated with soil organic matter and poorly crystalline Fe/Al minerals in soil, respectively. The total, pyrophosphate-extractable, and acid oxalate-extractable U concentrations were higher in the soil obtained from the NPK and NPK + compost sites than in that obtained from the control site. The difference in the U concentrations between the NPK or NPK + compost site and the control site corresponded with the increased U concentration observed after the application of the phosphate fertilizer or both the fertilizer and compost. In the upland field and pasture soil, the increase in pyrophosphate-extractable U was 83-94% of that in U_t. On the other hand, the increase in acid oxalate-extractable U was 44-58% of that in U_t in the upland field and pasture soil, but it was almost equivalent to the increase in U_t in the paddy soil with NPK. In conclusion, most of the phosphate fertilizer-derived U was either incorporated into the soil organic matter or poorly crystalline Fe/Al minerals in the surface soil of agricultural fields. Thus, soil organic matter is an important pool of U in upland field and pasture soil, whereas poorly crystalline Fe/Al minerals are important pools of U in paddy soil experiencing alternating changes in redox conditions.     

Concentrations, sources, and spatial distribution of individual polycyclic aromatic hydrocarbons (PAHs) in agricultural soils in the Eastern part of the EU: Poland as a case study

Soils from agricultural areas receive unsatisfactory attention as regards the contamination with organic pollutants. To answer those needs the contents of the sixteen individual PAH compounds were determined (GC/MS technique) in agricultural soils in Poland. The samples (n = 216) were collected from the upper layer of arable land in the year 2005. Half of the samples represented typical rural areas, while the rest derived from the territories potentially subjected to the urban/industrial pressure of various intensity. The mean (geometric) content of individual compounds varied from 1 μg kg^− 1 for acenaphtylene to 55 μg kg^− 1 for fluoranthene with the highest contributions (11.6%-12.9%) of phenanthrene, fluoranthene and pyrene. Higher molecular weight PAHs (4 rings) were strongly linked mutually and with the ∑16PAHs. They contributed substantially (73%) to the overall content of PAHs, which implies domination of anthropogenic sources. The calculated molecular indexes suggest that most of those PAHs derive from the combustion of coal, the main energy source in Poland. Simultaneously, the concentrations of lower molecular weight compounds seem to reflect the background, “natural” PAH compounds, which represent mainly atmospherically distributed emission. The division of the samples into groups describing geographical regions and landscape type enabled evaluation of the spatial trends in contamination of soils with PAH compounds. The most pronounced effect of spatial parameters corresponded to PAHs > 4 rings, while lower molecular weight compounds showed more homogeneous concentration through the country.